采用荧光光谱法和紫外可见吸收光谱法系统的研究了水溶性ZnO量子点(QDS)的光学性能及其与不同的生物大小分子的作用。研究发现,QDS除了具有普通量子点所具有的优点外,它还具有两个窄的荧光特征发射峰(分别在353和517nm),并与牛血清白蛋白(BSA)、L-苯丙氨酸(L-Phe)、DL-色氨酸(DL-Try)、L-组氨酸(L-His)等生物分子之间均能形成配合物。荧光光谱显示,L-His对QDS在517nm处的荧光有猝灭作用;而BSA则对QDS在353nm处的荧光具有显著的荧光增敏作用,并使QDS的发射峰发生红移(从353nm移至359nm)。QDS对L-Phe,DL-Try及BSA的荧光产生不同程度的猝灭作用,并且使DL-Try的荧光特征发射峰发生红移(从350nm移至359nm),而使BSA的荧光特征发射峰发生紫移(从336nm移至326nm)。其中,QDS对BSA分子的猝灭机制为静态猝灭。应用生物大小分子与QDS作用后的紫外可见吸收光谱,进一步证实了它们与量子点的结合。QDS与生物大小分子的作用表明,QDS可以对这几种生物分子进行跟踪标记,它通过和组成BSA的L-Phe,DL-Try,L-His等氨基酸小分子作用而与BSA作用的。
The sensitization effect of sodium dodecyl benzene sulfonate(SDBS) on the fluorescence of pyrene and anthracene was observed obviously,and the magnitude of increase in fluorescence intensity was found to keep linear relationships with the concentration of pyrene in the range of 4.9×10-9-5.0×10-8mol·L-1 and anthracene in the range of 5.6×10-9-5.6×10-8mol·L-1.Values of detection limit(3S/N) found were 7.4×10-10mol·L-1 for pyrene and 3.7×10-10mol·L-1 for anthracene.The reaction was used for determination of pyrene and anthracene and was applied to the analysis of river water,tap water and lake water,giving values of recovery in the range of 91.0%-102.0%(for pyrene) and 90.0%-111.1%(for anthracene).
ZnO quantum dots were synthesized by Sol-gel method in non-aqueous system. The resultant ZnO quantum dots were coated by 3-Aminopropyl triethoxysilane (APTES) to obtain water-solube ZnO/Aminopropylsiloxane quantum dots (ZnO-AS QDs). The optimum coating conditions are determined to be as t = 60 degrees C, T = 30 min, n(Si):n(Zn) = 1:1, V-PEC/V-total = 1/9. Two fluorescence emission peaks at 348 and 512 nm are observed, which may be excited in the 220-360 nm excitation range. While the ZnO quantum dots are coated by APTES, it is shown that the fluorescence emission intensity increases obviously with the same excitation range. After being coated, the ZnO quantum dots show good water-solubility up to 60 d, as well as good stability of the fluorescence properties in aqueous solution. The calculation results from the Bras equation show that the coating not only modifies ZnO quantum dots but also plays a protective role to restrain particle arrangement: The composition and core-shell structure of ZnO-AS QDs are confirmed by XRD and TEM, and the size of core is calculated to be 6 nm, the size of particle is 20 nm. Furthermore, different colors of ZnO-AS QDs were prepared by adjusting the particle size of ZnO core.
The interaction of bovine serum albumin(BSA) with water soluble ZnO quantum dots(QDS) was investigated by fluorescence spectroscopy.The fluorescence spectra shows that the addition of BSA results in the fluorescence intensity enhancement and red shift(from 353 nm to 359 nm) in the maximum emission peak of QDS,which indicates that there is interaction between BSA and QDS.On the other hand,the fluorescence of BSA quenched and blue-shifted(from 336 nm to 326 nm) in the presence of QDS,which further confirmed the interaction of BSA and QDS.The change in absorption spectrum and fluorescence spectrum was probably caused by the coordination and electrostatic interaction between QDS and BSA.The interaction of BSA with QDS indicates that QDS could label BSA.The mechanism has also been discussed according to fluorescence quenching effect of QDS on BSA.
Fiber dusts of three different areas were analyzed by XRF and samples were reacted with Lysozyme.The results show that Lysozyme has reacted with the substances in the samples.The UV-Vis and Fluorescent Spectra study was conducted on the reaction between the simulated ion and Lys,which found that the reaction between Lysozyme and element Fe3+,Pb2+ in the samples was obvious at 37 ℃.In UV-vis spectra the Lys-Fe3+absorption was strengthened and the Lys-Pb2+ maximum absorption peak red shifted 13 nm.In Fluorescent spectra,the Lys-Fe3+maximum fluorescence intensity appeared at the λem 450 nm and the fluorescence peak red shifted 30 nm,the Lys-Pb2+ maximum fluorescence intensity appeared at the λem 725 nm and the fluorescence peak red shifted 205 nm.
Fluorescence method was applied to the determination of anthracene and pyrene.The calibration curve linear ranges of anthracene and pyrene were 5.6×10-9—2.8×10-6mol/L and 4.9×10-8—1.47×10-6mol/L,respectively.Correlative coefficient was obtained as 0.99959 and 0.99822.The effect of common ion,temperature and time on the fluorescence intensity were studied.The no interference of common ions were for determination.Under the experiments conditions of 2 hours,5—55℃,the intensity of fluorescence was stable.Therefore this method has a wide range for temperature.can be used to detect anthracene and pyrene straight in non water system such as food,drink and liquor.
The binary oxalate precursor was prepared by solid-state reaction at room temperature with Zn(NO3)2·6H2O,Fe(NO3)2·9H2O,Oxalic acid and PVA as soft template.Then,the red-brown powders were characterized by SEM and XRD after calcination at 600 ℃ for 3 h.The results show that the one dimensional rod-like Zinc ferrite(ZnFe2O4) was obtained.Anthracene,pyrene and methylene blue were degraded with synthetic products,and the photocatalytic performance and effect were investigated by fluorescence and UV.The photocata-lytic degradation mechanism was discussed,and the effects of the catalyst amount,illumination time and the different illumination(natural light or ultraviolet light) on the photocatalytic process were investigated.As selection of optimum operation parameters,the degradation of efficiency of anthracene and pyrene were 95.19% and 96.46% respectively,the degradation efficiency of methylene blue was 48.93%.
The interactions of human serum albumin (HSA) with murexide (Mx) and murexide-copper complex (Mx-Cu2+) were investigated by fluorescence spectroscopy and Fourier transform infrared spectroscopy FTIR) under simulative physiological conditions. The results show Mx and Mx-Cu2+ could quench the intrinsic fluorescence of HSA by static quenching and hydrophobic interaction was the predominant intermolecular force. The binding constant of Mx and HSA was increased in the presence of copper (H). According to fluorescence resonance energy transfer (FRET), the distancer between donor (HSA) and acceptor (Mx and MxCu(2+)) were calculated to be 2.82 and 2.53 nm, the ternary system energy transfer efficiency E' > binary system E, which showed the copper ion acts as the energy transfer agency. The synchronous fluorescence and FTIR study suggested that Mx and Mx-Cu2+ can cause almost the same changes in the secondary structure of HSA. Upon binding with Mx or Mx-Cu2+, complex, the a-helix structure was reduced more than 8%, the beta-sheet reduced 1%, while the beta-turn increased 6%, and the random coil increased 4%. The results show that the main factor of secondary structure changing is Mx.
The interactions between human serum albumin(HSA) and acidic chromic blue K(ACBK) was investigated by fluorescence spectroscopy and Fourier transform infrared spectroscopy(FT-IR) under simulative physiological conditions.The quenching constants of HSA by ACBK suggested ACBK could quench the intrinsic fluorescence of HSA by static quenching.According to fluorescence resonance energy transfer(FRET),the distance and energy transfer efficiency(E) between the donor(HSA) and the acceptor(ACBK) were calculated to be 2.29 nm and 0.078,respectively.The relationship of fluorescence quenching and the changes of HSA secondary structure induced by ACBK binding was investigated by combining the results of fluorescence and FT-IR.The fluorescence results and FT-IR study suggested that hydrophobic interactions were the predominant intermolecular force and caused the secondary structure of HSA to change from α-helix and β-sheets to β-turns and random coils respectively.Upon HSA-ACBK complexing,the α-helix structure reduced by more than 9%,and the β-sheet reduced by 2%,while the β-turn increased by 6%,and the random coil increased by 5%.
A direct spectrofluorimetry method was established for simultaneous determination of dissolved pyrene(Py) and fluoranthene(FLuA) in water based on the great enhancement of fluorescence intensities of Py and FLuA in tween-20(Tw-20) medium.The effects of the types of surfactants,pH,and temperature on the systems were investigated.Under the optimized conditions,the calibration curves showed a good linear range from 1.98×10-10 to 9.88×10-8 mol/L for Py and 2.00×10-9 to 7.99×10-7 mol/L for FLuA,and their detection limits were 9.88×10-11 mol/L and 5.99×10-10 mol/L,respectively.The method was applied in the determination of Py and FLuA in real samples with satisfactory results.The recoveries of pyrene in tap water and river water were 92%-102% and 101%-102%,and the recoveries of fluoranthene in tap water and river water were 90%-100% and 94%-111%,respectively.The method is simple,rapid and sensitive for the determination of trace Py and FLuA in the real water sample.
As PAHs has a high Photoluminescent(PL) quantum yield and the solubilization and sensibilization effect of Nonionic surfactants on PAHs,a spectrofluorimetry has been established for Tween-80(TW-80) micellar sensitization of dissolved Anthracene(ANT) in water.The linear ranges for the determination of dissolved Anthracene was 1.6833×10-8~1.29×10-6 mol/L,the detection limits was 1.07×10-8mol/L.The method was highly sensitive.By using this method,real samples(tap water,river-water,lake-water) were determined directly and good results were obtained.The recovery of river-water was 94.6%~109.5%,the recovery of lake-water was 90.5%~106.9%,and the recovery of tap-water was 86.9%~111.7%.The method is rapid,sensitive,and simple to forecast and manage the pollution of water.
The characteristics of binding reaction between bovine serum albumin (BSA) and zincon (ZCN) were studied by fluorescence spectra and ultraviolet-visible absorption spectra. The bovine serum albumin can emit fluorescence (lamda(em) = 345 nm) under irradiation of ultraviolet light (lamda(ex) = 280 nm). After the zincon (ZCN) was added into BSA solution the fluorescence of BSA was quenched partially. The results indicated that ZCN was strongly bound to BSA. According to Stern-Volmer equation and Lineweaver-Burk equation, the quenching constant and the thermodynamic parameters were obtained. From the thermodynamic parameters the binding power between ZCN and BSA can be judged. The binding distance (r = 5.07 nm) and energy transfer efficiency (E = 0.67) between donor (BSA) and acceptor (ZCN) were obtained by Forster's non-radiative energy transfer mechanism. It is confirmed that the combination reaction between ZCN and BSA is a single static quenching process, and their interaction may be interpreted with energy transfer mechanism.
The interaction mechanism of diethylmalonylurea(BBT) with bovine serum albumin(BSA) was studied by fluorescence and UV-Vis spectra. It is shown that BBT has a powerful ability to quench the fluorescence intensity of BSA. The fluorescence quenching data were analyzed according to Stern-Volmer equation and Line weaver-Burk equation at 17 ℃ and 37 ℃ to obtain the quenching constants, 17 ℃KSV=1.427×104 and 37 ℃KSV=1.195×104, 17 ℃KLB=9.848×103 and 37 ℃KLB=1.778×103, and the binding constant K0=4.341×104, and the thermodynamic parameters(ΔH, ΔS and ΔG). It was deduced that combining site n was 1.136. The increasing of temperature was favorable for the BBT-BSA interaction. According to the thermodynamic parameters, the major binding forces were determined. The effect of BBT on the conformation of BSA was analyzed via synchronous fluorescence spectroscopy.
The interaction of p-methoxyacetophenone(MAP) with human serum albumin(HSA) was investigated by fluorescence spectroscopy;UV—Visible absorbance spectroscopy and Fourier transform infrared spectroscopy(FT—IR) under simulative physiological conditions.The quenching constants of MAP to HSA at three different temperatures(304,307 and 310K) were 7.64×103,7.68×103 and 7.73×103 L·mol-1 respectively,which suggested MAP could quench the intrinsic fluorescence of HSA by dynamic quenching.The activation energy of the interaction between MAP and HSA was calculated to be 0.998 kJ·mol-1.Wavelength shifts in synchronous fluorescence spectroscopy had suggested that polarity environment of HSA was increased by the association of MAP with HSA.FT—IR study suggested that the secondary structure of HSA changed from αhelix and β-sheet.
The complex formed between bovine serum albumin(BSA) and alizarin red S(ARS) was separated and prepared by gel chromatography.The absorbances of the complex in an excess of ARS were measured at λ_(420 nm) and λ_(530 nm),respectively by UV-Vis spectrophotometer.The concentrations of ARS and BSA-ARS were then calculated according to the following simultaneous equations: A_(420)=4.89×103 c_(ARS)+3.06×104 c_(BSA-ARS),A_(530)=4.60×102 c_(ARS)+2.29×104 c_(BSA-ARS).According to the orthogonal experiment,the optimum diameter and length of the chromatographic column were 1.0 cm and 30 cm,the gel amount was 1.3 g,the sampling concentration and volume for ARS were 5×10(-3) mol·L(-1) and 1.5 mL and those for BSA were 1.49×10(-3) mol·L(-1) BSA and 1.5 mL,the elution flow rate was 0.33 mL·min(-1) and the separating degree was 1.25.The wavelength of the maximum absorption peak of BSA-ARS complex was at 530 nm.
The interaction of p-nitrophenol(PNP) with bovine serum albumin(BSA) was investigated by fluorescence and UV-visible absorbance spectroscopy under simulative physiological conditions.Fluorescence quenching of PNP to BSA was suggested as static quenching according to the modified Stern-Volmer equation.The thermodynamic parameters ΔH0(-28.061kJ·mol-1) and ΔS0(-14.331J·mol-1·K-1) were obtained, which indicated hydrogen bonds play an important role in stablizing the complex.The distancer(5.94nm) between donor(BSA) and acceptor(PNP) was obtained according to fluorescence resonance energy transfer(FRET).The effect of PNP on the conformation of BSA has been analyzed by means of UV-visible absorption spectra and synchronous fluorescence spectra.
SiO2/ZnO water-soluble quantum dots were prepared by modification of (3-mercaptopropyl) tri-ethoxysilicane. The emission spectral peak of exciton fluorescence was raised by about 4 times in comparison with that of the quantum dots obtained by direct SiO2 deposit on ZnO without modification. The introduction of hydrosulfide group(HS - ) on ZnO, renders the quantum dots good water solubility, unique fluorescent stability and anti-congregation even at higher NaCl concentration. The water soluble blue SiO2/ZnO quantum dots were also prepared by this method with some modification of the reaction conditions. The photogenic wavelength of this blue quantum dots was found to be 420 nm. The emission spectra were very symmetrical without obvious red tall. The full widths half maximum were only 46 nm.
The interaction between alizarin yellow R(AYR) and bovine serum albumin(BSA) was investigated in UV—Vis spectrophotometry in alkali buffer solution.The results show that AYR—BSA is a blue color coordination compound having a maximum absorption at 386 nm with a blue shift of about 108 nm compared to the AYR complex.The spectroscopy was set up for determination of Albumin using AYR.The analyzing results of the samples show that the recovery is 96.4%~106.6% for BSA and the relative standard deviations are 0.28%~1.13%.The research results of the interaction between AYR and BSA are basically accordant no matter by dual wavelength method,balance dialysis method or mono-wavelength method.At the point of 386 nm,the combination proportion of AYR—BSA coordination compound is nAYR :nBSA=51,the Molar absorptivity e is 9.12×103 L·mol-1·cm-1 and the condition equilibrium constant K is 8.13×105.
Manifold mixed precursors were prepared with Ni(CH3COO)(2)(.)4H(2)O, Co(CH3COO)(2)(.)4H(2)O, H(2)C(2)O(4)(.)2H(2)O and different surfactants by solid state reaction at room temperature; then they were put into a bain-marie to keep 2d at 60 degrees C. After these precursors analyzed by TG-DTA, and decomposed at 610 degrees C, the phase and topography of the thermolysis products were characterized by XRD, SEM. The nanometer composite oxide NiCo2O4 with different topography was obtained. The experimental results show that these surfactants act as soft-templates, they have evident effect on topography of products.
A mixed oxalate precursor of ZnFe2O4 was prepared from Fe(NO3)3·9H2O, Zn(NO3)2·6H2O and H2C2O4·2H2O by solid-state reaction at room temperature. According to Hass low, a circulating system of the chemical reactions was designed to determine the ΔH values of reactants and resultants in the reaction. The standard formation enthalpy of Fe2(C2O4)3·5H2O(ΔHf,Fe2(C2O4)3·5H2O(s)) was calculated with the ΔH values. An isopiestic reaction calorimeter with constant surrounding temperature was used, and hydrochloric acid (3 mol/L) was employed as the solvent for calorimetric experiments. The standard formation enthalpy ΔHf,Fe2(C2O4)3·5H2O(s) is -4 082.29 kJ/mol. The enthalpy of the solid state reaction to prepare the precursor of ZnFe2O4 was calculated to be 406.21 kJ/mol, indicating that the reaction is endothermic.